This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Communication pubs.acs.org/JACS
Hydrogen Gas-Mediated Deoxydehydration/Hydrogenation of Sugar Acids: Catalytic Conversion of Glucarates to Adipates Reed T. Larson,†,§ Andrew Samant,†,§ Jianbin Chen,†,§ Woojin Lee,† Martin A. Bohn,‡ Dominik M. Ohlmann,‡ Stephan J. Zuend,#,§ and F. Dean Toste*,†,§ †
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States California Research Alliance (CARA), BASF Corporation, Berkeley, California 94720 United States # BASF Corp., 46820 Fremont Boulevard, Fremont, California 94538, United States ‡ BASF SE, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany §
S Supporting Information *
ABSTRACT: The development of a system for the operationally simple, scalable conversion of polyhydroxylated biomass into industrially relevant feedstock chemicals is described. This system includes a bimetallic Pd/Re catalyst in combination with hydrogen gas as a terminal reductant and enables the high-yielding reduction of sugar acids. This procedure has been applied to the synthesis of adipate esters, precursors for the production of Nylon-6,6, in excellent yield from biomass-derived sources. Figure 1. Methods for converting aldaric acids to adipic acid or adipate esters.
T
he valorization of biomass is an ongoing challenge that has significant implications for sustainability of processes in the chemical industry.1 Most current commercial processes to utilize biomass focus on chemically simple lipid-based sources.2 In contrast, carbohydrate feedstocks such as cellulose and starch have a high degree of chemical complexity and can potentially be useful as precursors to complex, industrially relevant molecules.3 One attractive target that meets this criterion is adipic acid and its derivatives.4 This C6 monomer is synthesized in quantities of 2.5 M tonnes per year in order to produce Nylon-6,6.5 Currently, its production employs petroleum-derived starting materials and is responsible for a significant proportion of anthropogenic N2O emissions.6 As such, identification of economical routes for adipic acid production from biomass would be a significant development.7 Glucose is an attractive choice of starting material for this route, as it is abundant and inexpensive.4,8 Additionally, it can be readily oxidized to glucaric acid, which contains the carboxylic acid functionality of adipic acid. While the conversion of glucaric acid into adipic acid using hydrogen as the terminal reductant has been reported, the reaction required stoichiometric hydrogen bromide to promote the reaction, which is likely to lead to challenges in reactor materials as well as issues involving removal of brominated byproducts (Figure 1A).9 The deoxydehydration (DODH) of diols to olefins is a promising alternative, as it offers the possibility of achieving the desired transformation at nearneutral pH without the need for any halogen promoters.10−12 However, traditional DODH chemistry is not without drawbacks. First, the reaction generally shows a preference for cisdiols, deriving from the requirement to form a rhenium diolate intermediate. This constraint is highlighted by the fact that mucic © 2017 American Chemical Society
acid, an aldaric acid with two cis-diols in its open form, has been converted into adipate esters in a two step process (Figure 1B),13 while the DODH reaction of glucaric acid gave only 25% of the muconic ester. More importantly, most reported DODH chemistry is mediated by expensive terminal reductants such as triphenylphosphine or secondary alcohols. In recent years, there have been several promising reports of hydrogen-mediated DODH reactions on model systems.14,15 However, to date, reports of applying such conditions to efficiently convert relevant sugar acids into adipates are absent. Herein, we describe discovery and development of a catalyst system that directly provides adipates from glucose derivatives, in a single operation, using hydrogen as a terminal reductant (Figure 1C). We conducted initial studies to assess the viability of adipate production via DODH using the ethyl ester of D-glucarate-6,3lactone 1, which can be derived from calcium glucarate. Direct application of literature precedent using a secondary alcohol as reductant/solvent and MTO as catalyst showed promising yields of the initial DODH product 2-Et (Table 1, entry 1), but with a significant degree of charring and precipitation of solid byproducts.16 Changing the solvent to ethanol lowered the yield of 2-Et somewhat, but also produced a homogeneous solution at the end of the reaction. In subsequent experiments, palladium on carbon and H2 were added with the aim of achieving a one-pot reduction to the saturated lactone 3-Et. Received: July 25, 2017 Published: October 3, 2017 14001
DOI: 10.1021/jacs.7b07801 J. Am. Chem. Soc. 2017, 139, 14001−14004
Communication
Journal of the American Chemical Society Table 1. Optimization of Reaction Conditionsa
Entry
Catalyst(s)
Additives
H2 Pressure
Solvent
Reaction Time
Yield 2
Yield 3
Yield 4
Yield 5
1 2 3 4 5 6 7 8 9 10 11
10 mol % MeReO3 10 mol % MeReO3 10 mol % MeReO3, 2.5 mol % Pd/C 10 mol % MeReO3 10 mol % MeReO3, 2.5 mol % Pd/C 10 mol % MeReO3, 2.5 mol % Pd/C 10 mol % MeReO3, 2.5 mol % Pd/C 10 mol % KReO4, 2.5 mol % Pd/C 10 mol % KReO4, 2.5 mol % Pd/C 1 mol % KReO4, 0.75 mol % Pd/C 1 mol % KReO4, 0.75 mol % Pd/C
27 wt % activated C 3 mol % H3PO4, 27 wt % activated C
1 bar 1 bar 5 bar 5 bar 5 bar 5 bar 5 bar 5 bar
3-octanol EtOH EtOH EtOH EtOH EtOH EtOH EtOH MeOH MeOH MeOH
2h 5h 5h 5h 5h 5h 18 h 18 h 18 h 18 h 18 h
55%b 42%c 40%c 39%c 65%c -
trace 32%c 28%c 30%c -
18%d -
22%c 61%d 71%d,e 88% (83%)d,e,f
a
Reactions run at 0.75 mmol scale. b3-octyl ester. cethyl ester. dmethyl ester. eReaction run at 7.5 mmol scale and 1 M concentration. fIsolated yield of adipic acid from hydrolysis of crude product with 2 N HCl in parentheses.
reaction mixture further improved the process, affording dimethyl adipate in 88% overall yield (entry 11). We propose the Brønsted acid cocatalysts acts to facilitate the ring opening of 3-Et to the necessary open-form diol, which might increase the rate of the desired reaction and that the activated carbon acts as a scavenger for catalysts poisons or as a support for partially reduced rhenium species. With these optimized conditions in hand, we explored the substrate scope of the reaction. A variety of polyhydroxylated esters and lactones were competent substrates (Table 2).
Interestingly, while the yield of 2-Et improved under these conditions, complete reduction to the saturated product was not observed at 1 bar of hydrogen. However, both a hydrogen atmosphere and Pd/C were necessary to observe an improvement in yield, suggesting that in this system the palladium facilitates the reduction of the rhenium catalyst by H2 (Table 1, entries 2−5). While several factors might result in formation of the fully saturated ester using the combined Pd/Re/H2 system, we posited the lack of alkene hydrogenation derived from the low hydrogen pressure. Indeed, increasing the pressure of hydrogen to 5 bar provided saturated 3-Et, but in significantly lower yield (Table 1, entry 6) compared to the amount of 2-Et produced at 1 bar, even with prolonged reaction times (entry 7). This observation supports a hypotheses the rhenium catalyst is unstable to hydrogen and that the palladium catalyst is still active at higher pressures. Thus, we posited the carbon−rhenium bond in MTO might be problematic to its stability under the reactions conditions, and sought alternative catalysts. Accordingly, replacing MTO with potassium perrhenate resulted in reduction to the saturated lactone 3-Et, as well as some production of 4-Et due to ring-opening of this initial product followed by a second DODH/hydrogenation sequence (entry 8). Spurred on by these promising results, conditions that promoted the ring-opening reaction of 3-Et were explored in order to improve the yield of the desired diethyl adipate. During the synthesis of various potential substrates, we observed choice of esterifying alcohol had a significant impact on the equilibrium concentrations of various lactonized products based on glucaric acid. In particular, while esterification with ethanol favored isolation of 6,3-lactone 1, under similar conditions in methanol the 1,4-lactone 6 was isolated almost exclusively.17 Given the importance of the lactone/ester equilibrium on formation of the final adipate esters, methanol was examined as a solvent for the tandem DODH/hydrogenation reaction, resulting in a good yield of dimethyl adipate (5-Me) as well as some unsaturated intermediate 4-Me (entry 9). Studying various additives uncovered that addition of activated carbon resulted in full conversion to 5-Me and allowed the concentration of the reaction to be increased to 1 M. Furthermore, addition of catalytic phosphoric acid to the
Table 2. Substrate Scopea
a
Substrate left/product(s) right. Reaction conditions: 7.5 mmol substrate, 1 mol % KReO4, 3 mol % H3PO4, 0.75 mol % Pd/C, 25 wt % activated carbon, 5 bar H2, 7.5 mL MeOH, 150 °C, 18 h. b Substrate prestirred at 120 °C in MeOH for 3 h. c48 h reaction time.
Interestingly, under these reaction conditions the DODH reaction was completely selective for vicinal diols in the α,β positions of carboxylic acids and esters; reaction of an equimolar mixture of diethyl tartrate and 1,2-dodecanediol produced diethyl succinate in 89% yield without a trace of dodecane (eq 1). This is in stark contrast to previously reported DODH 14002
DOI: 10.1021/jacs.7b07801 J. Am. Chem. Soc. 2017, 139, 14001−14004
Communication
Journal of the American Chemical Society protocols, where substrates primarily consist of electronically neutral aliphatic diols.
Table 3. Metal Analysis of Residual Solids after DODH Reaction
The divergent reactivity observed in this system prompted us to investigate the possibility the reaction proceeds via a mechanism that differs from the retro-[3+2]-cycloaddition generally postulated for rhenium-catalyzed DODH reactions.18 One possibility is the ester moiety promotes a stepwise dehydration19/ketone reduction pathway via either an α- or βketoester, as palladium-catalyzed hydrogenations of both have been reported previously.20 However, subjecting ethyl acetoacetate to the reaction conditions resulted in only trace reaction, and while diethyl 2-oxoglutarate was fully decomposed on the time scale of the reaction, only traces of the expected DODH/ hydrogenation product were observed (Figure 2A).21
of rhenium species occurs to a significant extent over the course of the reaction under typical conditions, the active catalyst is likely a soluble species. Lastly, we recognized the importance of our catalytic system’s reliance on hydrogen as a means of avoiding alcoholic solvents. In contrast to previously reported DODH-based syntheses of adipates, our system had the potential to directly produce adipic acid in water. This would confer several advantages: reduction of solvent cost, generation of the most industrially relevant nylon precursor, and simplification of the purification process. Reaction of glucarodilactone under analogous conditions did indeed produce adipic acid, albeit in only 19% yield. Based on this promising result, we examined strategies to stabilize the catalyst, ultimately finding that prestirring the rhenium precatalyst with DMAP23 and increasing the amount of activated charcoal used resulted in a 72% yield of adipic acid (eq 2).
The combination of a rhenium(VII) catalyst and a palladiumon-carbon cocatalyst has allowed for the development a catalytic system to effect the high-yielding complete deoxygenation of 1,2diols using hydrogen gas as the terminal reductant. Key to the success of this chemistry was the choice of a rhenium catalyst sufficiently stable to the strongly reducing conditions, as well as the addition of Pd/C, which acts both as a cocatalyst for the DODH step and the catalyst for the reduction of the resulting olefin. This catalyst system enabled the conversion of glucaric acid into adipate esters, as well as direct conversion into adipic acid using water as the solvent. In the future, we look forward to further investigating and optimizing this system as a means to affect the important goal of converting readily available biomass into valuable chemical feedstocks that have, until now, been derived from petroleum sources.
Figure 2. (A) Competence of diol dehydration products. (B) Impact of electronic properties of styrene diols on reaction yield.
Having ruled out the intermediacy of ketonic dehydration products, we reasoned the ester group might facilitate the DODH reaction, either by serving as an electron-withdrawing group or by coordinating to the rhenium catalyst. In order to distinguish between these possibilities, ester-substituted styrene glycol 7 and styrene glycol (8) were subjected to the standard reaction conditions for 3 h, producing the fully hydrogenated products in 53% and 15% yield, respectively (Figure 2B). Additionally, a 1-h direct competition experiment between 7 and 8 produced the ester-containing product in 44% yield and only traces of ethylbenzene. We therefore propose the ester (or other electron withdrawing group) facilitates the reaction by accepting electron density from the vicinal carbon−oxygen σ orbital into its π* orbital. This effect lowers the energy of the transition state for carbon−oxygen bond cleavage.18a,22 We also examined whether active rhenium catalyst was a soluble species or if surface deposition was responsible for the change in catalytic activity. SEM-EDS analysis indicated that use of KReO4 in the DODH reaction was accompanied by significant precipitation of rhenium-containing species onto the Pdcontaining solid support (Table 3). However, when tetrabutylammonium perrhenate was used as precatalyst, essentially no Re could be detected on the residual solids, while still performing at a similar level to the potassium catalyst. Thus, while precipitation
■
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b07801. Procedures and spectral data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*
[email protected] ORCID
F. Dean Toste: 0000-0001-8018-2198 Notes
The authors declare the following competing financial interest(s): A provisional patent has been filed by UC Berkeley and BASF. 14003
DOI: 10.1021/jacs.7b07801 J. Am. Chem. Soc. 2017, 139, 14001−14004
Communication
Journal of the American Chemical Society
■
(12) Mo-catalyzed DODH: (a) Sandbrink, L.; Beckerle, K.; Meiners, I.; Liffmann, R.; Rahimi, K.; Okuda, J.; Palkovits, R. ChemSusChem 2017, 10, 1375. (b) Dethlefsen, J. R.; Lupp, D.; Teshome, A.; Nielsen, L. B.; Fristrup, P. ACS Catal. 2015, 5, 3638. (c) Hills, L.; Moyano, R.; Montilla, F.; Pastor, A.; Galindo, A.; Á lvarez, E.; Marchetti, F.; Pettinari, C. Eur. J. Inorg. Chem. 2013, 2013, 3352−3361. V-catalyzed DODH: (d) Gopaladasu, T. V.; Nicholas, K. M. ACS Catal. 2016, 6, 1901. (e) Nicholas, K. M.; Chapman, G., Jr Chem. Commun. 2013, 49, 8199. (13) (a) Shiramizu, M.; Toste, F. D. Angew. Chem., Int. Ed. 2013, 52 (49), 12905. See also: (b) Li, X.; Wu, D.; Lu, T.; Yi, G.; Su, H.; Zhang, Y. Angew. Chem., Int. Ed. 2014, 53, 4200. (14) (a) Gopaladasu, T. V.; Nicholas, K. M. ACS Catal. 2016, 6, 1901. (b) Ziegler, J. E.; Zdilla, M. J.; Evans, A. J.; Abu-Omar, M. M. Inorg. Chem. 2009, 48, 9998. (15) A heterogeneous Re/Pd system gave excellent yields in the DODH of simple diols, but only modest yields in the DODH of sugar alcohols, see: (a) Ota, N.; Tamura, M.; Nakagawa, Y.; Okumura, K.; Tomishige, K. Angew. Chem., Int. Ed. 2015, 54, 1897. (b) Ota, N.; Tamura, M.; Nakagawa, Y.; Okumura, K.; Tomishige, K. ACS Catal. 2016, 6, 3213. (c) Tazawa, S.; Ota, N.; Tamura, M.; Nakagawa, Y.; Okumura, K.; Tomishige, K. ACS Catal. 2016, 6, 6393. For an additional example of H2/Pd/Re reduction with perchlorate anion as the substrate, see: Hurley, K. D.; Shapley, J. R. Environ. Sci. Technol. 2007, 41, 2044. For a related example of polyol reduction using Re/Ir rather than Re/Pd, see Tomishige, K.; Nakagawa, Y.; Tamura, M. Selective Hydrogenolysis of C-O bonds Using the Interaction of the Catalyst Surface and OH groups. In Selective Catalysis for Renewable Feedstocks and Chemicals; Nicholas, K. M., Ed.; Topics in Current Chemistry Series 353; Springer International Publishing: Switzerland, 2014; pp 127−162. (16) Previously reported DODH systems utilize solvents such as benzenes, dioxane, or long chain alcohols, which tended to lead to undesired condensation of 1 to 2, effectively eliminating the vicinal diol functionality. (17) The ratio of 1,4 vs 6,3 lactone is equal in the absence of catalysts in both EtOH and MeOH. The isolation of 1 and 6 appears to result from a dynamic crystallization process wherein 1 selectively crystallizes from the mother liquor in EtOH, while the remaining soluble glucarate reequilibrates as 1 precipitates. The same holds true for 6 in MeOH. For previous isolation of these lactones, see: Kiely, D. E.; Chen, L.; Lin, T. H. J. Am. Chem. Soc. 1994, 116, 571. (18) For DFT studies on the mechanism of: Recatalyzed DODH see: (a) Gable, K. P.; Zhuravlev, F. A. J. Am. Chem. Soc. 2002, 124, 3970. (b) Qu, S.; Dang, Y.; Wen, M.; Wang, Z.-W. Chem. - Eur. J. 2013, 19, 3827. (c) Dethlefsen, J. R.; Fristrup, P. ChemCatChem 2015, 7, 1184. (d) Wu, D.; Zhang, Y.; Su, H. Chem. - Asian J. 2016, 11, 1565. (e) Vcatalyzed DODH: Galindo, A. Inorg. Chem. 2016, 55, 2284. (19) Korstanje, T. J.; Jastrzebski, J. T. B. H.; Gebbink, R. J. M. K. Chem. - Eur. J. 2013, 19, 13224. (20) (a) Krebs, A.; Bolm, C. Synlett 2011, 2011, 671. (b) Marrodan, C. M.; Berti, D.; Liguori, F.; Barbaro, P. Catal. Sci. Technol. 2012, 2, 2279. (c) Hattori, K.; Sajiki, H.; Hirota, K. Tetrahedron 2001, 57, 4817. (21) Additionally, α,β-dideuterated substrates showed washing out of deuterium at the β position but not the α position. Since formation of either of these intermediates should result in deuterium exchange at the α-position (by direct reduction of that position for the α-ketoester and by facile enolization of the β-ketoester), this observation further supports the idea that ketoester intermediates are not involved in product formation (see SI for details). (22) Theoretical studies have shown the exact nature of the transition state for deoxydehydration and dihydroxylation can vary significantly depending on the ligand set of the catalytic species. As such, any insight into the specifics of the relevant transition state is challenging to derive from analogy to known catalytic systems. For experimental demonstration of an asynchronous transition state in the [3+2] cycloreversion, see 18a. For a theoretical analysis of the favored dihydroxylation/ deoxydehydration transition states for various simple rhenium complexes, see: Deubel, D. V.; Frenking, G. J. Am. Chem. Soc. 1999, 121, 2021. (23) Li, X.; Zhang, Y. ChemSusChem 2016, 9, 2774.
ACKNOWLEDGMENTS This work was financially supported by BASF Corporation (Award Number 53093) and the NSF through the Center for Sustainable Polymers (CHE-1413862). The authors thank Dr. Selim Alayoglu for assistance with SEM/EDS measurements. SEM/EDS work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC0205CH11231.
■
REFERENCES
(1) (a) Shanks, B. H.; Keeling, P. L. Green Chem. 2017, 19, 3177. (b) Sheldon, R. A. J. Mol. Catal. A: Chem. 2016, 422, 3. (c) Wu, L.; Moteki, T.; Gokhale, A. A.; Flaherty, D. W.; Toste, F. D. Chem. 2016, 1, 32. (d) Deneyer, A.; Renders, T.; Van Aelst, J.; Van den Bosch, S.; Gabriëls, D.; Sels, B. F. Curr. Opin. Chem. Biol. 2015, 29, 40. (e) Tuck, C. O.; Pérez, E.; Horváth, I. T.; Sheldon, R.; Poliakoff, M. Science 2012, 337, 695. (2) (a) Thakur, D. S.; Kundu, A. J. Am. Oil Chem. Soc. 2016, 93, 1575. (b) Marshall, A.-L.; Alaimo, P. J. Chem. - Eur. J. 2010, 16, 4970. (c) Behr, A.; Westfechtel, A.; Gomes, J. P. Chem. Eng. Technol. 2008, 31, 700. (d) Wittcoff, H. A.; Reuben, B. G.; Plotkin, J. S. In Industrial Organic Chemicals; John Wiley & Sons, Inc.: Hoboken, NJ, 2012; pp 493−521. (3) (a) Dusselier, M.; Mascal, M.; Sels, B. F. Top. Curr. Chem. 2014, 353, 1. (b) Tong, X.; Ma, Y.; Li, Y. Appl. Catal., A 2010, 385, 1. (4) (a) Kruyer, N. S.; Peralta-Yahya, P. Curr. Opin. Biotechnol. 2017, 45, 136. (b) Bart, J. C. J.; Cavallaro, S. Ind. Eng. Chem. Res. 2015, 54, 567. (c) Van de Vyver, S.; Roman-Leshkov, Y. Catal. Sci. Technol. 2013, 3, 1465. (5) (a) Bart, J. C. J.; Cavallaro, S. Ind. Eng. Chem. Res. 2015, 54, 1. (b) Hermans, I.; Jacobs, P. A.; Peeters, J. Chem. - Eur. J. 2006, 12, 4229. (c) Lichtenthaler, F. W. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2000. (d) Musser, M. T. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2000. (6) (a) Thiemens, M. H.; Trogler, W. C. Science 1991, 251 (4996), 932. (b) Reimer, R. A.; Slaten, C. S.; Seapan, M.; Lower, M. W.; Tomlinson, P. E. Environ. Prog. 1994, 13, 134. (7) (a) Llevot, A.; Dannecker, P.-K.; von Czapiewski, M.; Over, L. C.; Söyler, Z.; Meier, M. A. R. Chem. - Eur. J. 2016, 22, 11510. (b) Harmsen, P. F. H.; Hackmann, M. M.; Bos, H. L. Biofuels, Bioprod. Biorefin. 2014, 8, 306. (8) Draths, K. M.; Frost, J. W. J. Am. Chem. Soc. 1994, 116, 399. (9) Boussie, T. R.; Dias, E. L.; Fresco, Z. M.; Murphy, V. J.; Shoemaker, J.; Archer, R.; Jiang, H. US8669397B2, March 11, 2014. (10) For a general reviews of deoxygenation of biomass, see: (a) Rogers, K. A.; Zheng, Y. ChemSusChem 2016, 9, 1750. (b) Raju, S.; Moret, M.-E.; Gebbinik, R. J. M. K. ACS Catal. 2015, 5, 281. (c) Boucher-Jacobs, C.; Nicholas, K. M. Top. Curr. Chem. 2014, 353, 163. (11) (a) Cook, G. K.; Andrews, M. A. J. Am. Chem. Soc. 1996, 118, 9448. (b) Vkuturi, S.; Chapman, G.; Ahmad, I.; Nicholas, K. M. Inorg. Chem. 2010, 49, 4744. (c) Arceo, E.; Ellman, J. A.; Bergman, R. G. J. Am. Chem. Soc. 2010, 132, 11408. (d) Shiramizu, M.; Toste, F. D. Angew. Chem., Int. Ed. 2012, 51, 8082. (e) Yi, J.; Liu, S.; Abu-Omar, M. M. ChemSusChem 2012, 5, 1401. (f) Liu, P.; Nicholas, K. M. Organometallics 2013, 32, 1821. (g) Raju, S.; Jastrzebski, J. T. B. H.; Lutz, M.; Gebbink, R. J. M. K. ChemSusChem 2013, 6, 1673. (h) Denning, A. L.; Dang, H.; Liu, Z.; Nicholas, K. M.; Jentoft, F. C. ChemCatChem 2013, 5, 3567. (i) Boucher-Jacobs, C.; Nicholas, K. M. ChemSusChem 2013, 6, 597. (j) Dethlefsen, J. R.; Fristrup, P. ChemSusChem 2015, 8, 767. (k) Sandbrink, L.; Klindtworth, E.; Islam, H.-U.; Beale, A. M.; Palkovits, R. ACS Catal. 2016, 6, 677. (l) Raju, S.; van Slagmaat, C. A. M. R.; Li, J.; Lutz, M.; Jastrzebski, J. T. B. H.; Moret, M.-E.; Gebbink, R. J. M. K. Organometallics 2016, 35, 2178. (m) Shin, N.; Kwon, S.; Moon, S.; Hong, C. H.; Kim, Y. G. Tetrahedron 2017, 73, 4758. 14004
DOI: 10.1021/jacs.7b07801 J. Am. Chem. Soc. 2017, 139, 14001−14004
